Synthesis of new thiophenolato hydrido iron(II) complexes and their substitution reactions with alkynes

Article abstract of DOI:10.1016/j.poly.2009.08.005

The novel thiophenolato hydrido iron(II) complexes [cis-Fe(H)(SAr)(PMe₃)₄] (4-6) (Ar = p-BrC₆H₄ (4), p-MeOC₆H₄ (5) and o-MeC₆H₄ (6)) were prepared through the reaction

Full text of DOI:10.1016/j.poly.2009.08.005

Polyhedron 28 (2009) 3823–3827
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Polyhedron
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Synthesis of new thiophenolato hydrido iron(II) complexes and their
substitution reactions with alkynes
Tingting Zheng a, Min Li a, Hongjian Sun a, Klaus Harms b, Xiaoyan Li a,
*
a School of Chemistry and Chemical Engineering, Shandong University, Shanda Nanlu 27, 250100 Jinan, People’s Republic of China
b Department of Chemistry, University of Marburg, Hans-Meerwein-Strasse, 35032 Marburg, Germany
a r t i c l e i n f o
a b s t r a c t
Article history:
The novel thiophenolato hydrido iron(II) complexes [cis-Fe(H)(SAr)(PMe3)4] (4–6) (Ar = p-BrC6H4 (4), p-
MeOC6H4 (5) and o-MeC6H4 (6)) were prepared through the reaction of Fe(PMe3)4 with thiophenols ArSH
(1–3). Reaction of 6 with trimethylsilylacetylene and phenylacetylene afforded bisalkynyl iron(II) com-
plexes [Fe(PMe3)4(C„CSiMe3)2] (7) and [Fe(PMe3)4(C„CPh)2] (9) through elimination of dihydrogen
and the formation of thiophenol. The reaction of 5 with 2-methyl-3-butyn-2-ol gave [Fe(PMe3)4(C„CC-
Me2OH)2] (10). The crystal structures of complexes 4, 7 and 10 were determined by X-ray diffraction. A
mechanism for the formation of 7 is proposed.
Received 2 June 2009
Accepted 6 August 2009
Available online 12 August 2009
Keywords:
Hydrido iron complex
Trimethylphosphine
Thiophenol
Ó 2009 Elsevier Ltd. All rights reserved.
Crystal structure
1. Introduction
We have reported on the S–H bond activation of thiophenols at
cobalt(0) and cobalt(I) centres [21]. A novel thiophenolato hydrido
Hydrido compounds of transition metals are not only important
materials in many stoichiometric reactions, but also decisive inter-
mediates in catalytic processes. Therefore, they play an important
role in synthetic and industrial chemistry. Literature reports on
transition metal hydrides are mainly concentrated on precious
metals such as Ru, Rh, Ir, Pt, Pd [1–13]. For their lighter congeners
Fe, Co and Ni, there are rather few reports with regard to catalytic
properties of their metal hydrides, which would be of great signif-
icance from the perspective of economic practicality.
cobalt(III) complex was obtained (Eq. (1)). As continuation of this
work we here report on progress in the S–H bond activation by
iron(0). The novel hydrido iron complexes (4–6) formed by oxida-
tive addition of S–H moieties were isolated and characterized.
Reaction of the hydrido iron complexes with alkynes invariably re-
sulted in bisalkynyl iron(II) complexes. No insertion products have
been observed that dominated reactions of hydrido cobalt [22] and
hydrido nickel [15] complexes.
2. Experimental
A [MꢀH] moiety in hydrido compounds of transition metals can
react with alkenes or alkynes giving rise to
r-alkyl or r-alkenyl
2.1. General procedures and materials
metal compounds. It has been demonstrated that hydrides of co-
balt and nickel afforded the expected products, while the family
iron hydrides has received less attention [14,15].
More recently, vinyl sulfides have shown great potential in or-
ganic synthesis with the useful feature of a unique selectivity con-
trol. They are easily obtained by reaction of thiols with alkynes
[16–18], and it was recognized that the addition of thiol to alkyne
in the presence of a metal catalyst occurs with high regioselectivity
and good yields [19,20].
Standard vacuum techniques were used in manipulations of
volatile and air-sensitive materials. The literature method was
used in the preparation of tetrakis(trimethylphosphane)iron(0)
[23]. Other chemicals were used as purchased. Infrared spectra
(4000–400 cmꢀ1), as obtained from Nujol mulls between KBr disks,
were recorded on a Nicolet 5700. 1H, 13C, and 31P NMR (300, 75,
and 121 MHz, respectively) spectra were recorded on a Bruker
Avance 300 spectrometer. 13C and 31P NMR resonances were ob-
tained with broadband proton decoupling. X-ray crystallography
was performed with a Bruker Smart 1000 diffractometer.
SPh
Co(PMe3)4
PMe3
PMe3
Me3P
H
Co
ð1Þ
Co(PMe3)3Cl
Co(PMe3)4Me
PhSH
+
2.2. Synthesis of the complexes
SPh
2.2.1. Synthesis of 4
To a solution of 1.10 g (3.05 mmol) of Fe(PMe3)4 in 50 mL of pen-
tane was slowly injected 0.58 g (3.07 mmol) of p-bromothiophenol
* Corresponding author. Tel./fax: +86 531 88361350.
E-mail address: xli63@sdu.edu.cn (X. Li).
0277-5387/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.poly.2009.08.005

3824
T. Zheng et al. / Polyhedron 28 (2009) 3823–3827
1 at ꢀ80 °C. The reaction started immediately with formation of a
yellow solid. The mixture was allowed to warm to ambient temper-
ature. During this period the color turned yellow-brown. After
stirring at room temperature for 16 h a dark brown solution was ob-
tained. After a slight turbidity had been filtered off, the red filtrate
at 4 °C gave red crystals of 4 suitable for X-ray diffraction. Yield:
0.28 g (17%). Anal. Calc. for C18H41BrFeP4S (549.21 g/mol): C,
39.36; H, 7.52. Found: C, 39.02; H, 8.01%. IR (Nujol, cmꢀ1): 1866
tered off, and from the brown filtrate at 4 °C yellow cubic crys-
tals of 9 were obtained. Yield: 0.23 g (25%). Anal. Calc. for
C28H46FeP4 (562.41 g/mol): C, 59.80; H, 8.24. Found: C, 59.90;
H, 8.01%. IR (Nujol, cmꢀ1): 2037
m(C„C), 1589 m(C@C), 936
m
(PMe3). 1H NMR (300 MHz, C6D6, 296 K, ppm): d 1.41 (m,
36H, PCH3), 6.96–7.41 (m, 10H, Ar–H); 31P NMR (121 MHz,
C6D6, 300 K, ppm): d 20.9 (s, PCH3).
m
(Fe–H), 1580 m(C@C), 939 m
(PMe3). 1H NMR (300 MHz, C6D6,
2.2.6. Synthesis of 10
296 K, ppm): d 0.99 (m, 36H, PCH3), 7.16–8.09 (m, 4H, Ar–H),
ꢀ10.31 (m, 1H, Fe–H); 31P NMR (121 MHz, C6D6, 300 K, ppm): d
10.1 (m, 1P), 16.6 (m, 2P), 27.6 (m, 1P).
To a solution of 0.82 g (1.64 mmol) of complex 5 in 50 mL of
pentane at ꢀ80 °C were slowly injected 0.28 g (3.33 mmol) of 2-
methyl-3-butyn-2-ol. The reaction mixture was allowed to warm
to ambient temperature. After stirring at room temperature for
16 h the color of the solution changed to yellow-brown. A slight
turbidity was filtered off, and from the yellow filtrate at 4 °C yel-
low cubic crystals of 10 were obtained. Yield: 0.43 g (25%). Anal.
Calc. for C22H50FeO2P4 (526.38 g/mol): C, 50.20; H, 9.57. Found:
2.2.2. Synthesis of 5
To a solution of 1.24 g (3.44 mmol) of Fe(PMe3)4 in 50 mL of
pentane was slowly injected 0.48 g (3.44 mmol) of p-methoxylthi-
ophenol 2 at ꢀ80 °C. The reaction started immediately with forma-
tion of a yellow solid. The reaction mixture was allowed to warm
to ambient temperature. During this period the color turned yel-
low-brown. After stirring at room temperature for 16 h a dark
brown solution was obtained. A slight turbidity was filtered off,
and from the red filtrate at 4 °C red crystals of 5 were obtained.
Yield: 0.43 g (25%). Anal. Calc. for C19H44FeOP4S (500.36 g/mol):
C, 45.61; H, 8.86. Found: C, 45.46; H, 9.00%. IR (Nujol, cmꢀ1):
C, 50.50; H, 9.55%. IR (Nujol, cmꢀ1): 1922
m(C„C), 938
m
(PMe3). 1H NMR (300 MHz, C6D6, 296 K, ppm): d 1.22 (m,
36H, PCH3), 5.00(s br, 1H, OH); 31P NMR (121 MHz, C6D6,
300 K, ppm): d 20.8 (s, PCH3).
2.3. X-ray structure determinations
1818
m(Fe–H), 1591 m(C@C), 942 m
(PMe3). 1H NMR (300 MHz,
C6D6, 296 K, ppm): d 1.12 (m, 36H, PCH3), 3.40 (s, 3H, OCH3),
7.15–8.22 (m, 4H, Ar–H), ꢀ14.20 (m, 1H, Fe–H); 31P NMR
(121 MHz, C6D6, 300 K, ppm): d 10.8 (m, 1P), 16.5 (m, 2P), 24.2
(m, 1P).
Intensity data were collected on a Bruker SMART diffractometer
with graphite-monochromated Mo K
a radiation (k = 0.71073 Å).
Crystallographic data for complexes 4, 7, and 10 are summarized
in Table 1. The structures were solved by direct methods and re-
fined with full matrix least-squares on all F2 (shelxl-97) with non-
hydrogen atoms anisotropic.
2.2.3. Synthesis of 6
To a solution of 1.37 g (3.80 mmol) of Fe(PMe3)4 in 50 mL of
pentane were slowly injected 0.47 g (3.79 mmol) of o-methylthio-
phenol 3 at ꢀ80 °C. The reaction started immediately with forma-
tion of a yellow solid. The reaction mixture was allowed to warm
to ambient temperature. During this period the color turned yel-
low-brown. After stirring at room temperature for 16 h a dark
brown solution was obtained. A slight turbidity was filtered off,
and from the red filtrate at 4 °C red crystals of 6 were obtained.
Yield: 0.51 g (28%). Anal. Calc. for C19H44FeP4S (484.36 g/mol): C,
47.12; H, 9.16. Found: C, 46.80; H, 8.88%. IR (Nujol, cmꢀ1): 1834
3. Results and discussion
3.1. Synthesis of hydrido phenylthiolato iron(II) complexes
Reaction of Fe(PMe3)4 with thiophenols 1–3 to gave rise to the
hydrido iron complexes 4–6 (Eq. (2)) via an oxidative addition of
the S–H bond.
At ꢀ27 °C crystalline solids were obtained with yields of 17–
28%. In the solid state complexes 4–6 rapidly decompose when ex-
posed to air.
m
(Fe–H), 1580 m(C@C), 937 m
(PMe3). 1H NMR (300 MHz, C6D6,
296 K, ppm): d 1.13 (m, 36H, PCH3), 2.87 (s, 3H, CH3), 7.16–8.66
(m, 4H, Ar–H), ꢀ9.99 (m, 1H, Fe–H); 31P NMR (121 MHz, C6D6,
300 K, ppm): d 10.4 (m, 1P), 16.4 (m, 2P), 27.5 (m, 1P); 13C NMR
(75 MHz, C6H6, 297 K, ppm): d 24.5 (m, PCH3), 30.5 (s, Ar–C),
119.3 (s, Ar–C), 125.0 (s, Ar–C), 131.3 (s, Ar–C).
Table 1
Crystallographic data for complexes 4, 7 and 10.
Complex
4
7
10 ꢁ 2
2.2.4. Synthesis of 7
Empirical formula
Formula weight
T (K)
Crystal system
Space group
a (Å)
C18H41BrFeP4S
549.21
100(2)
monoclinic
P21/c
13.8039(7)
28.913(2)
12.8157(7)
90
90.327(4)
90
5114.8(5)
8
C22H54FeP4Si2
554.55
293(2)
monoclinic
P21/c
16.024
10.587
20.696
90
112.05
90
3254.2
4
C44H100Fe2O4P8
1052.70
293(2)
monoclinic
C2/c
24.009
19.446
17.018
90
134.38
90
5678.6
4
To a solution of 0.50 g (1.03 mmol) of complex 6 in 50 mL of
pentane were slowly injected 0.21 g (2.14 mmol) of trimethylsi-
lylacetylene at ꢀ80 °C. After stirring at room temperature for
18 h a dark brown solution was obtained. A slight turbidity
was filtered off, and from the brown filtrate at 4 °C yellow cubic
crystals of 7 were obtained. Yield: 0.17 g (30%). Anal. Calc. for
C22H54FeP4Si2 (554.55 g/mol): C, 47.65; H, 9.81. Found: C,
b (Å)
c (Å)
a
(°)
47.86; H, 10.01%. IR (Nujol, cmꢀ1): 1968
m(C„C), 939 m(PMe3).
b (°)
1H NMR (300 MHz, C6D6, 296 K, ppm): d 1.42 (m, 36H, PCH3),
0.11 (d, 6H, CH3); 31P NMR (121 MHz, C6D6, 300 K, ppm): d
20.0 (s, PCH3).
c
(°)
V (Å3)
Z
DCalc (g cmꢀ3
)
1.426
1.132
1.231
Reflections measured
Unique reflections
Rint
24688
8974
0.2316
25.00
0.0830
0.1321
17323
6821
0.0916
27.04
0.0563
0.1709
12078
4880
0.0349
25.00
0.0919
0.2435
2.2.5. Synthesis of 9
To a solution of 0.80 g (1.65 mmol) of complex 6 in 50 mL of
pentane were slowly injected 0.34 g (3.33 mmol) of phen-
ylethyne at ꢀ80 °C. After stirring at room temperature for 18 h
a dark brown solution was obtained. A slight turbidity was fil-
hmax (°)
R1 (I > 2
r
(I))
wR2 (all data)

T. Zheng et al. / Polyhedron 28 (2009) 3823–3827
3825
PMe3
Fe
ido ligand in comparison with the thiolato donor the distance P7–
Fe2 (2.222(4) Å) is larger than the distance P8–Fe2 (2.184(4) Å).
These structural features are in accordance with phenolato iron
complexes [24]. The bond lengths are normal for transition metal
thiolates [25]. In complex 4 the Fe bonded hydrid atoms have been
located and refined riding on the Fe atoms with a common isotro-
pic temperature factor.
PMe3
PMe3
H
ArSH
Fe(PMe3)4
+
Ar
S
PMe3
1 - 3
4 - 6
ð2Þ
Ar = p-BrC6H4, p-MeOC6H4, o-MeC6H4
3.2. Reaction of 6 with trimethylsilylacetylene
1
4
2
5
3
6
Hydrido iron(II) complex 6 reacts with trimethylsilylacetylene
to give the bis(trimethylsilylethynyl)iron(II) complex 7 according
to Eq. (3).
In the infrared spectra of complexes 4–6, the characteristic
m
(Fe–H) bands are found at 1866, 1818 and 1834 cmꢀ1 because
SiMe3
the electron-withdrawing Br group at the para-position makes
the Fe–H bond stronger comparing with the electron-donating
methoxy group at the para-position. The electron-donating
methyl group on the ortho-position has less influence upon the
Fe–H bond. The resonances of the Fe–H group in the 1H NMR
spectra at room temperature are registered between ꢀ9.99 and
ꢀ14.20 ppm as a multiplet. The protons of the PMe3 groups res-
onate in the range of 0.99–1.13 ppm. In the 31P NMR spectra
three multiplets between 10.1–10.8 ppm, 16.4–16.6 ppm and
24.2–27.6 ppm are found with the intensity ratio of 1:2:1. This
confirms that two of the four PMe3 ligands have the same chem-
ical surrounding. The spectroscopic data are compatible with an
octahedral configuration around the Fe atom consisting of a P–
Fe–P axis and equatorial coordination of P, P, S and H atoms.
The expected molecular structure was confirmed by X-ray dif-
fraction analysis of complex 4 (Fig. 1).
PMe3
PMe3
PMe3
Me
SH
H
S
Me3P
Me3P
PMe3
PMe3
Fe
Me Si
H
2
+
Fe
3
o-MeC6H4
+
H2
PMe3
SiMe3
6
7
ð3Þ
Complex 7 is an entirely different reaction product where the
expected result [15,22] would be a vinyl compound. It can be
proposed that the stronger basicity of the hydrido hydrogen in
complex 6 is beneficial to the formation of H2 and complex 7.
In the IR spectra the characteristic
m(C„C) band was found at
1968 cmꢀ1. No absorption characteristic of a phenyl group was
identified. In the 1H NMR spectrum the singlet resonance of
SiMe3 protons is registered at 0.11 ppm while those of the
PMe3 ligands at 1.42 ppm also appear as singlet. In the 31P
NMR spectrum, the PMe3 group gave rise to a singlet signal at
20.0 ppm. Spectroscopic data are compatible with an octahedral
configuration around the iron atom consisting of a C–Fe–C axis
and equatorial P1, P2, P3, and P4 donor atoms. The molecular
structure of complex 7 was confirmed by single crystal X-ray dif-
fraction analysis.
The molecular structure of complex 4 shows an octahedral
geometry around the iron atom with atoms P5 and P6 in axial posi-
tions. The angle P5–Fe2–P6 of 162.75(16)° (Fig. 1) indicates the po-
sition of the hydrido ligand. H200, S2, P7, P6 are located in an
equatorial plane. Owing to the stronger trans-influence of the hydr-
The molecular structure of complex 7 is shown in Fig. 2, which
shows an octahedral geometry around the iron atom with two
alkynyl-C atoms in axial positions and four equatorial P-donor
atoms.
Br2
C22
In our earlier study cobalt and nickel hydrides reacted with
alkynes affording products of an insertion reaction [22,24]. With
C23
C21
C24
C20
C28
C19
H200
C30
P6
C27
S2
P5
C29
Fe2
C35
P8
C26
C36
C33
C31
P7
C32
C34
C25
Fig. 2. Molecular structure of 7 and selected bond distances (Å) and angles (°): C6–
Fe1 1.921(4), C1–Fe1 1.918(4), Fe1–P2 2.2359(8), Fe1–P1 2.2368(7), Fe1–P3
2.2410(8), Fe1–P4 2.2414(8), C2–C1 1.240(5), C6–C7 1.238(5); C1–Fe1–C6
179.8(1), C1–Fe1–P2 98.5(1) C6–Fe1–P2 81.3(1), C1–Fe1–P1 99.7(1), C6–Fe1–P1
80.5(1), P2–Fe1–P1 161.8(1), C1–Fe1–P3 81.2(1), C6–Fe1–P3 98.8(1), P2–Fe1–P3
91.5(1), P1–Fe1–P3 91.0(1), C1–Fe1–P4 80.5(1), C6–Fe1–P4 99.5(1), P2–Fe1–P4
91.7(1), P1–Fe1–P4 91.5(1), P3–Fe1–P4 161.7(1).
Fig. 1. Molecular structure of 4 and selected bond distances (Å) and angles (°): P5–
Fe2 2.248(3), P6–Fe2 2.279(3), P7–Fe2 2.222(4), P8–Fe2 2.184(4), Fe2–H200 1.5091,
S2–Fe2 2.355(4); P8–Fe2–P7 99.0(2), P8–Fe2–P5 93.6(1), P7–Fe2–P5 95.1(1), P8–
Fe2–P6 99.5(1), P7–Fe2–P6 93.9(1), P5–Fe2–P6 162.8(2), P8–Fe2–S2 165.8(2), P7–
Fe2–S2 95.0(1), P5–Fe2–S2 83.3(1), P6–Fe2–S2 81.3(1), P8–Fe2–H200 81.5, P7–Fe2–
H200 179.4, P5–Fe2–H200 85.1, P6–Fe2–H200 85.8, S2–Fe2–H200 84.5.

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T. Zheng et al. / Polyhedron 28 (2009) 3823–3827
PMe3
Fe
PMe3
Fe
Me3Si
PMe3
H
S
PMe3
PMe3
SiMe3
+
H
o-MeC6H4
PMe3
H2
o-MeC6H4
S
PMe3
PMe3
6
8
Me3P
Me3P
PMe3
SiMe
H
+
3
Me3Si
Fe
PMe3
SiMe3
o-MeC6H4SH
7
Scheme 1. Proposed mechanism of reaction (3).
PMe3
iron hydrides reactivity is turned towards substituted products.
A possible reaction mechanism is proposed in Scheme 1. In the
first step, trimethylsilylacetylene reacts with a [Fe–H] function
by elimination of dihydrogen yielding intermediate (8) which
can react with another trimethylsilylacetylene molecule through
elimination of thiophenol to give the bisalkynyl iron(II) complex
7 as end product.
PMe3
PMe3
H
S
Fe
HO
H
2
+
p-MeOC6H4
PMe3
5
OH
ð5Þ
3.3. Reaction of 6 with phenylacetylene
Me3P
Me3P
PMe3
Pentane
H2
Fe
p-MeOC6H4SH
+
PMe3
When phenylethyne was used in the reaction of complex 6,
complex 9 was directly obtained from pentane as yellow cubic
crystals (Eq. (4)). Complex 9 is stable in the air for several hours
at room temperature.
HO
10
PMe3
PMe3
PMe3
H
S
Fe
C H
6
2
H
+
5
The molecular structure of complex 10 is shown in Fig. 3, which is
similar with complex 7. The bending of [C„C–C]-chain away from
180° and some differences in Fe–P distances in complex 7 and 10
should be attributable to packing effects in the crystal structures.
o-MeC6H4
PMe3
6
C6H5
Fe
ð4Þ
Me
SH
Me3P
Me3P
PMe3
PMe3
+
H2
C6H5
9
In the IR spectrum of complex 9 the characteristic
m(C„C) band
is registered at 2037 cmꢀ1. The PMe3 protons resonate at 1.41 ppm.
In the 31P NMR spectrum a singlet for the PMe3 ligands was found
at 20.9 ppm. The spectroscopic data are compatible with an octa-
hedral configuration around the iron atom.
3.4. Reaction of 5 with 2-methyl-3-butyn-2-ol
By reaction of complex 5 with 2-methyl-3-butyn-2-ol under
similar conditions complex 10 was obtained as yellow cubic crys-
tals (Eq. (5)). In the IR spectrum of 10 the typical
t(C„C) absorp-
tion appears at 1922 cmꢀ1, and the
t(O–H) band is registered at
3442 cmꢀ1. The 1H NMR spectrum shows PMe3 protons as multi-
plet at 1.22 ppm. In the 31P NMR spectrum a singlet was found at
20.8 ppm for the PMe3 ligands. The spectroscopic data are compat-
ible with an octahedral configuration around the iron atom con-
sisting of a C–Fe–C axis and equatorial coordination of P1, P2, P3,
and P4 donor atoms. The molecular structure of complex 10 was
confirmed by X-ray diffraction analysis.
Fig. 3. Molecular structure of 10 and selected bond distances (Å) and angles (°):
Fe1–C1 1.955(8), Fe1–C1A 1.955(8), Fe1–P1 2.224(2), Fe1–P1A 2.224(2), Fe1–P2A
2.232(2), Fe1–P2 2.232(2), P1–C9 1.820(9), P1–C8 1.834(9), P1–C7 1.848(9), P2–C10
1.833(9), P2–C11 1.840(9), P2–C12 1.855(10); C1–Fe1–C1A 176.5(4), C1–Fe1–P1
98.2(2) C1A–Fe1–P1 79.4(2), C1–Fe1–P1A 79.4(2), C1A–Fe1–P1A 98.2(2), P1–Fe1–
P1A 92.1(1), C1–Fe1–P2A 101.6(2), C1A–Fe1–P2A 80.9(2), P1–Fe1–P2A 160.3(1),
P1A–Fe1–P2A 91.6(1), C1–Fe1–P2 80.9(2), C1A–Fe1–P2 101.6(2), P1–Fe1–P2
91.6(1), P1A–Fe1–P2 160.3(1), P2A–Fe1–P2 91.5(1).

T. Zheng et al. / Polyhedron 28 (2009) 3823–3827
3827
4. Conclusion
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an expected insertion reaction have been observed.
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CCDC 711798, 711796, and 711797 contain the supplementary
crystallographic data for 4, 7 and 10. These data can be obtained
free of charge via http://www.ccdc.cam.ac.uk/conts/retriev-
ing.html, or from the Cambridge Crystallographic Data Centre, 12
Union Road, Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-033;
or e-mail: deposit@ccdc.cam.ac.uk.
Acknowledgments
We gratefully acknowledge support by NSF China Nos.
20872080/20772072 and Science Foundation of Shandong Prov-
ince Nos. Y2007B06/Y2006B18. We also thank Prof. Dieter Fenske
(University of Karlsruhe, Germany) for kind assistance with the
X-ray diffraction analysis.
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